The present invention relates to certain hydrocarbon soluble or dispersible hydroxy ether amine friction modifying additives for oleaginous compositions including fuel oil and lubricating oils, such as greases, industrial oils, gear oils, power transmitting fluids, engine lubricating oils, and particularly automatic transmission fluids, and to the oleaginous compositions in which they are contained.
There are many instances, as is well known, particularly under boundary lubrication conditions where two moving surfaces in contact with each other must be lubricated, or otherwise protected, so as to prevent wear, and to insure continued movement. There are other instances where friction between two rubbing surfaces is sought to be modified but not necessarily minimized. By controlling friction between two surfaces, the power required to impart movement from one surface to another is also controlled.
For example, a specialized property sought to be imparted to certain lube oil compositions adapted for use as an automatic transmission fluid is the friction modification characteristic of the fluid. This property distinguishes automatic transmission fluids (ATF) from other lubricants, and in fact between types of ATFs as well. Such characteristic quality has received the most attention by both the transmission manufacturers and fluid producers for many years. This attention stems from the fact that the friction requirements of an ATF are unique and depend on the transmission and clutch design, as well as on the type of clutch plate material used.
Another property sought to be imparted to lubricating oil compositions including automatic transmission fluids is reduced wear such as bearing and power component wear.
As is also well known, both wear and friction modification can be controlled through the addition of suitable additives with varying degrees of success.
While there are many known additives which may be classified as anti-wear, or friction modifying agents, it is also known that many of these additives act in a different physical or chemical manner and often compete with one another, e.g. they may compete for the surface of the moving metal parts which are subjected to lubrication. Accordingly, extreme care must be exercised in the selection of these additives to insure compatibility and effectiveness.
The metal dihydrocarbyl dithiophosphates are one of the additives which are known to exhibit anti-oxidant and anti-wear properties. The most commonly used additives of this class are the zinc dialkyl dithiophosphates (ZDDP) which are conventionally used in lubricant compositions. While such zinc compounds afford excellent oxidation resistance and exhibit superior anti-wear properties, they can be corrosive.
Both anti-wear and friction modifying agents function by forming a coating on the surface of the moving metal parts. The coating bonds are generally affected physically and/or chemically. Consequently, if the bonding between the anti-wear agent and the metal part is stronger than the bonding between the friction modifying agent and the metal part, the anti-wear agent will displace the friction modifying agent at the metal surface, i.e. at the metal/fluid lubrication boundary interface. This results in a loss in the ability of the friction modifying agent to exert its intended effect.
Various tests have been designed by auto manufacturers for measuring ATF friction and anti-wear properties to evaluate the performance of additives in view of the requirements of particular transmission designs and their ability to impart transmission durability and smooth shifting under a variety of road conditions.
Friction modification is typically evaluated on an SAE No. 2 friction apparatus. In this test, the motor and flywheel of the friction machine (filled with fluid to be tested) are accelerated to constant speed, the motor is shut off and the flywheel speed is decreased to zero by application of the clutch. The clutch plates are then released, the flywheel is again accelerated to constant speed, and the clutch pack which is immersed in the test fluid is engaged again. This process is repeated many times with each clutch engagement being called a cycle.
During the clutch application, friction torque is recorded as a function of time. The friction data obtained are either the torque traces themselves or friction coefficients calculated from the torque traces. The shape of the torque trace desired is set by the auto manufacturers. One way of expressing this shape mathematically is to determine the torque: (a) when the flywheel speed is midway between the maximum constant speed selected and zero speed (such torque measurement is referred to herein as T.sub.D) and (b) when as the flywheel speed approaches zero rpm (such torque measurement is referred to herein as T.sub.O). Such torques can then be used to determine the torque ratio which is expressed as T.sub.O /T.sub.D, or alternatively, to determine the torque differential which is expressed as T.sub.O -T.sub.D. The optimum target values for torque ratio and torque differential are set by the auto manufacturers. As the T.sub.O /T.sub.D increasingly exceeds 1, a transmission will typically exhibit shorter harsher shifts as it changes gears. On the other hand as T.sub.O /T.sub.D decreases below 1, there is an increasingly greater danger of clutch slippage when the transmission changes gears. Similar relationships exits with respect to a T.sub.O -T.sub.D target value of 0.
While many automatic transmission fluids can achieve target values of T.sub.O /T.sub.D after a minimum number of cycles, it becomes increasingly more difficult to sustain such target values as the number of cycles are increased. The ability of an ATF to sustain such desired friction properties is referred to herein as friction stability or durability. A high level of friction stability is difficult to achieve with ATFs containing certain anti-wear additives. It is believed that as the ATF ages under the influence of the heat of friction, the anti-wear agent can break down and the decomposition products displace conventional friction modifiers at the metal/fluid lubrication boundary interface. As a result, the fluid may exhibit varying friction properties.
Attempts to improve friction stability by simply adding more friction modifier have not met with success because this tends to reduce the breakaway static torque (T.sub.S) of the fluid. This parameter when expressed as the breakaway static torque ratio (T.sub.S /T.sub.D) reflects the relative tendency of engaged parts, such as clutch packs, bands and drums, to slip under load. If this value is too low, the slippage can impair the driveability and safety of the vehicle.
Very recently, more stringent requirements relating the automatic transmission fluids have been set by one or more auto manufacturers. The desire to enhance fuel economy has resulted in downsizing of cars and power trains, smaller engines and higher shift speeds, and increased usage of torque converter clutches, sprag clutches, and a shift to front wheel drive.
Thus, transmission designs have undergone radical changes, thereby necessitating the formulation of ATF additives capable of meeting new and more stringent property requirements needed to match such design changes.
No base oil alone can even approach the many special properties required for ATF service. Consequently, it is necessary to employ several chemical additives, each of which is designed to impart or improve a specific property of the fluid. Consequently, it becomes particularly advantageous when one additive can perform more than one function, thereby reducing the number of additives needed to be present in the formulation.
Accordingly, there has been a continuing search for new additives possessed of one or more properties which render them suitable for use in ATF compositions, as well as other oleaginous compositions. There also has been a search for new combinations of additives which not only provide ATF compositions, as well as other oleaginous compositions, with the various specific properties that are required, but which are compatible with each other in the sense that they do not exhibit any substantial tendency to compete with each other, nor to otherwise reduce the effectiveness of the various additives in the compositions. The present invention was developed in response to this search.
U.S. Pat. No. 2,290,880 discloses ethers of alcohol amines which may be used as interface modifying agents in a wide variety of arts. The compounds are said to be useful in lubricating oils and the like, thus enabling the production of effective boring oils, cutting oils, drilling oils, wire drawing oils, extreme pressure lubricants and the like.
U.S. Pat. No. 3,255,253 discloses amine-containing polyols which are prepared by first cyanoethylating an alcohol in the presence of a basic catalyst. The cyanoethylated alcohol is then hydrogenated to produce a primary amine, whereafter the primary amine is reacted with an alkylene oxide in the presence of a basic catalyst to form the desired amine-containing polyol. The amine-containing polyols are said to be useful for preparing polyurethane products, as hardeners for polyepoxide resins, and in the preparation of coatings and plasticizers.
U.S. Pat. No. 3,456,012 relates to polyolefin adducts of gamma-alkoxypropylamines having surfactant properties.
U.S. Pat. No. 3,464,925 relates to hydraulic fluids which contain certain aminotriols. The aminotriols are obtained by heating propylene oxide and triisopropylamine under pressure, in the presence of an alkaline catalyst.
U.S. Pat. No. 3,705,139 discloses alkyl sulfide compounds of the formula: EQU R.sub.1 -S-R-.sub.2 -A-(R.sub.3 O)-.sub.n Z,
where R.sub.1 represents a hydrocarbyl radical having 6 to 22 carbon atoms, R.sub.2 and R.sub.3 each represents a hydrocarbyl radical having 1 to 4 carbon atoms, A can represent nitrogen, n represents an integer in the range of 0-100, and Z can represent hydrogen. The alkyl sulfide compounds are disclosed as being antistatic agents.
U.S. Pat. No. 4,201,684 relates to lubricating oil adapted for use as a crankcase lubricant in internal combustion engines containing a friction reducing amount of a sulfurized fatty acid amide, ester or ester-amide of an oxyalkylated amine.
U.S. Pat. No. 4,231,883 relates to the use of an alkoxylated hydrocarbyl amine in a lubricating oil or fuel to reduce the friction of an internal combustion engine in which the lubricating oil or fuel is used. An example of the alkoxylated hydrocarbyl amine compounds that are disclosed in this patent is N,N-bis(2-hydroxyethyl) oleylamine.
U.S. Pat. No. 4,486,324 discloses an aqueous hydraulic fluid comprising at least 80% water and containing a hydrocarbyl-substituted succinic acid, a zinc dihydrocarbyl dithiophosphate, a hydroxyalkylamine, sodium alkyl benzene sulfonate, and optionally, a polyalkylene glycol mono-fatty acid ester.
U.S. Pat. No. 4,650,865 relates to a process for preparing tertiary ether amines which exhibit surface active properties. The tertiary ether amines may be used as surfactants and as starting materials for the production of surface active derivatives, such as for example, amineoxides and quaternary ammonium compounds.
U.S. Pat. No. 4,129,508 relates to lubricant and fuel compositions characterized by improved demulsifying properties. The patent discloses an automatic transmission fluid which includes a number of additives including a dialkyl phosphite, the reaction product of a polyisobutenyl-substituted succinic anhydride, commercial tetraethylene pentamine, and boric acid prepared as set forth in U.S. Pat. No. 3,254,025, and a conventional friction modifier based on bishydroxyethyl tallow amine (Ethomeen T/12), the reaction product of polyisobutenyl succinic anhydride and an ethylene polyamine, and Ethomeen C/15.
U.S. Pat. No. 2,151,300 relates to lubricating oil compositions which contain a major proportion of a mineral lubricating oil, a minor proportion of an organic phosphite such as triphenyl phosphite, and a small amount, sufficient to bring about substantial stability of the phosphorous compound, of an oil-soluble organic amine.
U.S. Pat. No. 4,634,543 relates to a fluid composition for use in a shock absorber. The fluid composition comprises a lubricating base oil, a boron-containing compound, and a phosphoric acid ester and/or phosphorous acid ester, such as diphenyl hydrogenphosphite.
U.S. Pat. No. 3,645,886 relates to the concept of reducing or preventing the fouling of process equipment in petroleum or chemical industries wherein an organic feed stock is subjected to heat exchange at a temperature of from about 200.degree. to about 1300.degree. F., and there is added to that organic feed stock a mixture of a fatty acid ester of an alkanol amine and a mono-, di-, or triorganic phosphite ester. The triorganic phosphite esters may include triphenyl phosphite.
U.S. Pat. No. 3,484,375 discloses the production of additives for lubricating oils, middle distillate fuels, residual fuels or reduced crudes in order to improve their resistance to oxidation, sludge formation, to improve their viscosity index, or to improve their flowability and pour point characteristics. The additives are prepared by reacting an organic phosphite ester with an alkaline polyamine or aminoalcohol. The preferred organic phosphite esters contain at least one hydroxyl group attached to the phosphorous, but they may include triphenyl phosphite.
U.S. Pat. No. 4,170,560 discloses additive compositions for use in crankcase lubricating oils comprising a mixture of an oil soluble anti-oxidant and an oil soluble hydroxylamine which includes both the Ethomeens and the Ethoduomeens. (Sold by the Armak Company, part of Akzona, Inc.).
U.S. Pat. No. 4,529,528 discloses the reaction product of, for example, an Ethomeen, a dialkyl phosphite and a boron compound.
U.S. Pat. No. 4,382,006 discloses a lubricating composition containing a friction reducing portion of a borated adduct of compounds which include the Ethomeens.
U.S. Pat. No. 2,917,160 discloses the use of certain hydroxylated tertiary amines which include the Ethomeens, as a corrosion inhibiting surface active lubricant for metal working. The amines may be used in the form of a salt. Phosphoric acid salts are illustrated.
U.S. Pat. No. 3,186,946 discloses cutting fluids in which the active lubricating component is a borate salt of a tertiary amine which includes both the Ethomeens and the Ethoduomeens.
U.S. Pat. No. 4,557,845 discloses the reaction product of an Ethomeen and a di-(C.sub.1 -C.sub.6 hydrocarbyl) phosphite. The reaction product is formed at a temperature between about 80.degree. and 280.degree. C., and in reactant proportions suc that from about 5 to 100% of the amine hydroxy groups are reacted with the phosphite.
U.S. Pat. No. 3,509,052 relates to lubricating compositions containing a lubricating oil, a dispersant which is a derivative of a substituted succinic acid, and a demulsifier. The demulsifier may comprise, for example, an Ethomeen, but the preferred demulsifiers are polyoxyalkylene polyols and derivatives thereof.
U.S. Pat. No. 3,394,179 discloses an oil soluble lubricant additive which is the reaction product of a phosphosulfurized hydrocarbon and an amide which is formed by reacting an aliphatic polyamine with a high molecular weig monocarboxylic acid. The phosphosulfurized hydrocarbon is prepared by reacting a terpene, a petroleum fraction or a polymer of a C.sub.2 -C.sub.6 olefin with a sulfide of phosphorous.
U.S. Pat. No. 2,805,217, relates to condensation products of terpenes with phosphorous sesquisulfide and oxygen. The condensation products are employed in lubricating oil compositions as anti-oxidants and detergents.
U.S. Pat. No. 3,511,780 relates to an additive that is useful as a sludge dispersant, anti-wear agent, anti-oxidant and inhibitor of harmful deposit formation in hydrocarbon compositions including fuel oils and lubricants. The additive is prepared by condensing an alkenyl succinic anhydride with an aliphatic polyamine or with an aliphatic polyamine and a carboxylic acid, followed by further reaction of the condensation product with a phosphosulfurized hydrocarbon and with a dialkyl dithiophosphoric acid. A suitable phosphosulfurized hydrocarbon is exemplified by P.sub.2 S.sub.5 -treated polyisobutylene.
U.S. Pat. No. 3,850,822 discloses a lubricating oil for an internal combustion engine comprising a major portion of oil and a minor portion of an additive package which includes a dispersant, a phosphosulfurized olefinic hydrocarbon, and a phosphorothionyl disulfide of phenol or of a C.sub.1 -C.sub.18 alkyl phenol. In one embodiment, the dispersant is made by the reaction of a polyisobutenyl succinic anhydride with a tetraethylene pentamine, the phosphosulfurized olefinic hydrocarbon is made from the reaction of P.sub.2 S.sub.5 with alpha-pinene, and the phosphorothionyl disulfide is that of a nonyl phenol.
U.S. Pat. No. 4,557,845 discloses that the products of reaction between a 2-hydroxyethyl alkylamine or certain higher oxylated members, and a dihydrocarbyl phosphite compound are effective friction modifiers and fuel reducing additives for internal combustion engines when such products are compounded with lubricants and liquid fulls. A similar disclosure is contained in U.S. Pat. No. 4,529,528, except that the products are prepared by reacting a bis(2-hydroxyethyl) alkylamine, a dihydrocarbyl phosphite and a boron compound.
U.S. Pat. No. 3,175,976 relates to automatic transmission fluids of improved high temperature stability. The fluids contain a light oil in combination with a di(tertiary-butyl) phenol, a zinc dialkyl dithiophosphate and an alkyl methacrylatevinyl pyrrolidone copolymer.
U.S. Pat. No. 3,933,659 relates to extended life functional fluids which are useful in automatic transmissions. The functional fluids of this patent comprise a major amount of an oil of lubricating viscosity and an effective amount of an alkenyl succinimide, a Group II metal salt of a dihydrocarbyl dithiophosphoric acid, a basic sulfurized alkaline earth metal alkyl phenate, and a compound selected from the group consisting of (a) fatty acid esters of dihydric and other polyhydric alcohols, and oil soluble oxyalkylated derivatives thereof, (b) fatty acid amides of low molecular weight amino acids, (c) N-fatty alkyl-N,N-diethanol amines, (d) N-fatty alkyl-N,N-di(ethoxyethanol) amines, (e) N-fatty alkyl-N,N-di(polyethoxy) ethanol amines, and (f) mixtures thereof.
U.S. Pat. No. 4,010,106 relates to a functional fluid which is useful in automatic transmissions and which comprises an oil of lubricating viscosity, and an effective amount of each of the following: an alkenyl succinimide, a Group II metal salt of a dihydrocarbyl dithiophosphoric acid, a friction modifier, a basic sulfurized alkaline earth metal alkyl phenate, and a chlorinated olefin containing from about 15 to 50 carbon atoms, from 20 to 60% by weight chlorine, and having a boiling point of at least about 300.degree. F. Among the friction modifiers which may be used in the functional fluid there are mentioned fatty acid esters of a polyhdryic alcohol or oil soluble oxyalkylated derivatives thereof, fatty acid amides of low-molecular weight amino acids, N-fatty alkyl-N,N-diethanol amine, N-fatty alkyl-N,N-di(ethoxyethanol)amines, N-fatty alkyl-N,N-di(polyethoxy) ethanol amines or mixtures thereof.
U.S. Pat. No. 4,208,293 discloses lubricating oil compositions adapted for use as a crankcase lubricant in internal combustion engines containing a friction reducing amount of a fatty acid amide or ester of diethanolamine. The compositions show improved results when they contain a zinc dihydrocarbyl dithiophosphate. Other additives may be included in the compositions, and among the additives which are mentioned in this patent are alkaline earth metal phenates and sulfurized phenates, alkaline earth hydrocarbyl sulfonates, phosphosulfurized terpene and polyolefins and their alkaline earth metal salts, poly-alkyl methacrylate or ethylene-propylene copolymers, ethylene-propylene non-conjugated diene terpolymers, and 4,4'-methylenebis(2,6-di-tert-butylphenol).
U.S. Pat. No. 4,474,674 discloses the use of diethanolamides or diisopropanolamides of alkyl thioglycolic acids or boron, phosphorous or metal reaction products thereof as multifunctional additives for power transmission shift fluids such as automatic transmission fluids. These additives provide the properties of anti-oxidation, H.sub.2 S suppression, corrosion inhibition and friction modification.
U.S. Pat. No. 2,806,022 discloses neutralizing the reaction products of a phosphorus sulfide and hydrocarbon with a basic metal compound. The neutralized products are used as lubricating additives in the preparation of lubricants for internal combustion engines.
U.S. Patent 2,316,080 relates to lubricants for use in internal combustion engines such as automobile and diesel engines under severe conditions wherein corrosion, piston ring sticking, cylinder wear, and carbon and/or varnish formation may be encountered. The lubricants comprise a lubricating oil and a small amount of a neutralized or partially neutralized reaction product of a phosphorus sulfide and a mono-olefinic hydrocarbon polymer. This neutralized or partially neutralized product, or a metal derivative thereof, may be used in lubricating oils alone or in combination with the non-neutralized phosphorus sulfide-olefin polymer reaction product. The neutralization of phosphorus sulfide-olefin polymer reaction product may be effected by adding to the reaction product a suitable alkaline compound such as a hydroxide, a carbonate or an oxide of an alkali or alkaline earth metal, and preferably potassium hydroxide. Ammonia or alkyl or aryl substituted ammonia such a amines may be used. Similar disclosures are contained in U.S. Pat. Nos. 2,316,082 and 2,316,088.
U.S. Pat. No. 3,034,907 discloses compositions of matter which are effective agents for hindering or retarding rust formation on iron surfaces and ice formation in the intake system of internal combustion engines. The compositions are characterized by a content of (a) a hydrophobic organic carrier, (b) a carboxylic acid amide monocarboxylic acid and (c) and an at least equivalent amount of a hydroxyalkylated nitrogen base which contains at least one lipophilic radical. The hydroxyalkylated nitrogen base corresponds to the general formula: ##STR2## wherein L represents a lipophilic radical defined above, X represents a bridging member which is bound to the nitrogen atom by means of an aliphatic carbon atom and which is selected from the group consisting of lower --O-alkylene, --S-alkylene, --O-hydroxyalkylene, --S-hydroxyalkylene, and ##STR3## wherein R'=H, low molecular alkyl or low molecular hydroxyalkyl, --CO--O--alkylene and --CO--O--hydroxyalkylene radicals. In the above formulas, n represents the integer 0 or 1, R.sub.1 represents hydrogen, a lower alkyl or lower hydroxyalkyl or lower aminoalkyl radical, and R.sub.2 is the same as (L-X.sub.n) and R.sub.1. In all cases, at least one of the radicals X, R.sub.1 and R.sub.2 is a lower hydroxyalkylated aliphatic radical.
U.S. Pat. No. 3,235,501 relates to oil compositions which contain a detergent which promotes foaming, a silicone polymer anti-foamant and a small amount of a foam inhibiting polyalkyl oxylated aliphatic amine. The polyalkyl oxylated aliphatic amines conform to one of the following formulas "a" or "b" depending on whether the amine from which they are prepared is a mono- or diamine: ##STR4## where R is an aliphatic radical of from about 4 to 24 carbon atoms, --R'O-- is an alkylene oxide radical selected from the group consisting of ethylene oxide and propylene oxide radicals, n is an integer from 1 to about 25 and X is selected from hydrogen, R and --(R'O).sub.2 H radicals, the total value of n in any instance being no greater than 25, and ##STR5## where R" is an aliphatic radical having from 2 to about 6 carbon atoms, R'O, n and X are defined in Formula "a" but at least one X is an R radical, and the total value of n in any instance being no greater than about 25. Among the detergents which are disclosed in the patent are the oil soluble metal salts of high molecular weight (300-1000) sulfonic acids, such as petroleum derived sulfonic acids and synthetic alkyl-aryl sulfonic acids having from about 8 to about 24 carbon atoms in the alkyl portion thereof, the normal or basic (complex or over-based) barium and calcium sulfonate salts, the metal salts of alkylphenol sulfides, such as, for example, the normal or basic (complex) barium and calcium salts of amyl and nonyl-substituted phenol sulfides, and the metal salts of phosphorous sulfide-hydrocarbon reaction products. Specific salts of this character are the metal salts of phosphosulfurized polyolefins, such as the barium salts of P.sub.2 S.sub.5 -polypropylene reaction products. Salts of this type are fully described for example the above-discussed U.S. Pat. Nos. 2,316,080, 2,316,082, 2,316,088 and 2,806,022.
U.S. Pat. No. 4,664,826 relates to metal salt esters of hydrocarbyl-substituted succinic acid or anhyride, such as octadecenyl succinic anhydride, and alkanols, such as thio-bis-ethanol, which are capable of exhibiting friction modification, oxidation inhibition, and corrosion inhibition properties in power transmitting fluids such as automatic transmission fluids.
U.S. Pat. No. 4,704,217 relates to a gasoline crankcase lubricant which contains as a friction modifier a dialkoxylated alkyl polyoxyalkyl amine of the formula: ##STR6## wherein R is a (C.sub.1 -C.sub.20) hydrocarbyl radical, R' and R'' are divalent (C.sub.1 -C.sub.10) alkylene groups, a is an integer of about 1 to about 10, and x+y is a value of about 1 to about 20.